Natural Oil Derivatives Including (Meth)acrylate Functional Groups

ABSTRACT

A compound has Structure I: 
     
       
         
         
             
             
         
       
     
     where R 1  and R 2  independently are C 2 -C 12  alkyl groups, R 3  and R 3 ′ independently are H or CH 3 , X 1  is a C 4 -C 28  alkyl or alkenyl group, and R 4  is H or a N,N-bis((meth)acryloylalkyl)-amide group having Structure II: 
     
       
         
         
             
             
         
       
     
     where R 5  and R 6  independently are C 2 -C 12  alkyl groups, and R 3 ″ and R 3 ′″ independently are either H or CH 3 .

REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/783,269 entitled “Natural Oil Derivatives Including (Meth)acrylateFunctional Groups” filed Mar. 14, 2013, which is incorporated byreference in its entirety.

BACKGROUND

Compounds having one or more (meth)acrylate functional groups are usedin a wide variety of applications, and particularly in preparingpolymers and copolymers. (Meth)acrylate functional groups include bothacrylate functional groups having the structure —O—C(═O)—CH═CH₂, andmethacrylate functional groups having the structure —O—C(═O)—C(CH₃)═CH₂.

Examples of acrylates include but are not limited to alkyl acrylatessuch as methyl acrylate, ethyl acrylate, propyl acrylate, butylacrylate, 2-ethylhexyl acrylate, lauryl acrylate and hexadecyl acrylate;functionalized alkyl acrylates such as hydroxyethyl acrylate,hydroxypropyl acrylate, carboxyethyl acrylate, sulfopropyl acrylate,(2-(acryloyloxy)ethyl)trimethyl ammonium chloride and polyethyleneglycolacrylate. Polyacrylate materials typically are used as coatings and asadditives to fluids, lubricants and surface sealants.

Examples of methacrylates include but are not limited to alkyl acrylatessuch as methyl methacrylate, ethyl methacrylate, propyl methacrylate,butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate andhexadecyl methacrylate; functionalized alkyl methacrylates such ashydroxyethyl methacrylate, hydroxypropyl methacrylate, carboxyethylmethacrylate, sulfopropyl methacrylate,(2-(methacryloyloxy)ethyl)trimethyl ammonium chloride andpolyethyleneglycol methacrylate. Polymethacrylate materials typicallyare used as rigid plastics and as transparent glazing materials.

Acrylate and methacrylate compounds also are used as comonomers withother types of monomers in preparing copolymers. As acrylate andmethacrylate monomers can undergo addition copolymerization with eachother and/or with a variety of conventional alkene-functional monomers,the potential applications of (meth)acrylate compounds in polymerchemistry are numerous and diverse.

In addition, compounds having one or more (meth)acrylate functionalgroups also are used to form dendritic molecules. Dendritic moleculesmay be used as solubility enhancers, as catalyst supports, asimmunoassay components, and as precursors for advanced materials.Species of the poly(amido amine) (PAMAM) class of dendrimers typicallyare formed by alternating reaction of ethylenediamine and methylacrylate. Examples of PAMAM dendrimers include but are not limited to[NH₂(CH₂)₂NH₂]:(G=0);dendri PAMAM(NH₂)₄ and its associated highergeneration molecules.

The physical and chemical properties of polymers and of dendriticmolecules are affected by the chemical structures of the building blocksused to prepare the polymers and/or dendritic molecules. Alteration ofthe chemical structure, size and/or concentration of these buildingblocks can allow for modification of the properties of the polymer ordendritic molecule.

It is desirable to expand the chemical structures present in compoundshaving one or more (meth)acrylate functional groups, so as to expand theuseful properties that can be provided by polymers or dendriticmolecules formed from the compounds. With regard to polymers, forexample, properties such as flexibility, toughness, etc. can beincreased by incorporating chemical groups that lower the modulus orthat can absorb energy, respectively. This expansion of chemicalstructures may be accomplished through post-polymerization processing,such as reaction with other reagents or blending with other polymers. Itis especially desirable, however, to expand the chemical structures byintroducing new chemical structures in the monomeric building blocksfrom which the polymer is formed. With regard to dendritic molecules,properties such as solubility, chemical reactivity, density, etc. can bechanged by incorporating branches having different chain lengths andsubstitution points.

One potential approach to altering the chemical structure of compoundshaving one or more (meth)acrylate functional groups is to form thecompounds from renewable feedstocks. Renewable feedstocks, such as fattyacids or fatty esters derived from natural oils, have opened newpossibilities for the development of a variety of industrially usefulsubstances, including specialty chemicals and intermediates. Forexample, renewable feedstocks can be used to prepare compounds havingcombinations of properties that were not available with conventionalpetroleum feedstocks. In another example, renewable feedstocks can beused to prepare compounds more efficiently, without requiringundesirable reagents or solvents, and/or with decreased amounts of wasteor side products.

It would be desirable to provide compounds having one or more(meth)acrylate functional groups that include previously unavailablechemical structures. Preferably such compounds can be used assubstitutes for conventional (meth)acrylate-functionalized compounds,while providing an increase in the renewable content of the finalproduct formed using the compounds. Preferably such compounds canprovide useful combinations of properties that are difficult to obtainusing compounds formed from conventional petroleum feedstocks.

SUMMARY

The scope of the present invention is defined solely by the appendedclaims, and is not affected to any degree by the statements within thissummary.

In one aspect, a compound is provided that has Structure I:

where R₁ and R₂ independently are C₂-C₁₂ alkyl groups, R₃ and R₃′independently are either H or CH₃, X₁ is a C₄-C₂₈ alkyl or alkenylgroup, and R₄ is selected from the group consisting of H and aN,N-bis((meth)acryloylalkyl)amide group represented by Structure II:

where R₅ and R₆ independently are C₂-C₁₂ alkyl groups, and R₃″ and R₃′″independently are either H or CH₃.

In another aspect, a ((meth)acryloylalkyl)amide composition is providedthat includes the reaction product of a (hydroxyalkyl)amide and a(meth)acryloyl halide, where the (hydroxyalkyl)amide is a reactionproduct of a metathesized natural oil and a bis(hydroxyalkyl)amine.

In another aspect, a method of making a ((meth)acryloylalkyl)amidecomposition is provided that includes forming a first reaction mixtureincluding a metathesized natural oil and a bis(hydroxyalkyl)amine,forming a first product mixture including a (hydroxyalkyl)amide formedfrom the metathesized natural oil and the bis(hydroxyalkyl)amine,forming a second reaction mixture including the (hydroxyalkyl)amide anda (meth)acryloyl halide, and forming a second product mixture includinga ((meth)acryloylalkyl)amide.

In another aspect, a method of making a polymer is provided thatincludes forming a polymerization mixture containing a first monomercontaining a compound having Structure I, and forming a product mixturecomprising a polymer comprising constitutional units formed from thefirst monomer.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention can be better understood with reference to the followingdrawings and description. The components in the figures are notnecessarily to scale and are not intended to accurately representmolecules or their interactions, emphasis instead being placed uponillustrating the principles of the invention. Moreover, in the figures,like referenced numerals designate corresponding parts throughout thedifferent views.

FIG. 1 depicts a reaction scheme for a metathesis reaction of a naturaloil.

FIG. 2 depicts a method of making a ((meth)acryloylalkyl)amide.

FIG. 3 depicts a representative reaction scheme for a method of forminga ((meth)acryloylalkyl)amide.

FIG. 4 depicts a method of making a polymer.

FIG. 5 depicts a representative reaction scheme for a method of forminga copolymer.

DETAILED DESCRIPTION

To provide a clear and more consistent understanding of thespecification and claims of this application, the following definitionsare provided.

The terms “reaction” and “chemical reaction” refer to the conversion ofa substance into a product, irrespective of reagents or mechanismsinvolved.

The term “reaction product” refers to a substance produced from achemical reaction of one or more reactant substances.

The term “alkyl group” refers to a group formed by removing a hydrogenfrom a carbon of an alkane, where an alkane is an acyclic or cycliccompound consisting entirely of hydrogen atoms and saturated carbonatoms.

The term “alkenyl group” refers to a group formed by removing a hydrogenfrom a carbon of an alkene, where an alkene is an acyclic or cycliccompound consisting entirely of hydrogen atoms and carbon atoms, andincluding at least one carbon-carbon double bond. A compound containingan alkenyl group is conventionally referred to as an “unsaturatedcompound”.

The term “functional group” refers to a group that includes one or aplurality of atoms other than hydrogen and sp³ carbon atoms. Examples offunctional groups include but are not limited to hydroxyl (—OH),protected hydroxyl, ether (—C—O—C—), ketone (>C═O), ester (—C(═O)O—C—),carboxylic acid (—C(═O)OH), cyano (—C≡N), amido (—C(═O)NH—C—),isocyanate (—N═C═O), urethane (—O—C(═O)—NH—), urea (—NH—C(═O)—NH—),protected amino, thiol (—SH), sulfone, sulfoxide, phosphine, phosphite,phosphate, halide (—X), and the like.

The term “(meth)acrylate group” refers to a functional group having thestructure —O—C(═O)—CR═CH₂), where R is H or CH₃. The term“(meth)acrylate group” includes both methacrylate groups (R═CH₃) andacrylate groups (R═H).

The terms “(meth)acryloylalkyl” and “(meth)acryloylalkyl group” refer toa functional group formed by removing a hydrogen from an alkyl carbonatom in an organic (meth)acrylate compound (R′—O—C(═O)—CR═CH₂), where R′is an alkyl group and R is H or CH₃. The term “(meth)acryloyl group”includes both methacryloylalkyl groups (R═CH₃) and acryloylalkyl groups(R═H).

The terms “amide”, “amide group” and “amido group” refer to a groupformed by removing a hydrogen from a carbon atom and/or removing one orboth hydrogens from the nitrogen of an organic amide (R—C(═O)—NH₂)compound, where R is an organic group. A primary amide group may berepresented by the structural formula —C(═O)—NH₂, a secondary amidegroup may be represented by the structural formula —C(═O)—NH—R′, and atertiary amide group may be represented by the structural formula—C(═O)—NR′R″, where R′ and R″ are organic groups.

The term “((meth)acryloylalkyl)amide” refers to a compound that includesa least one alkyl and/or alkenyl group, at least one amide group, and atleast one (meth)acryloylalkyl group bonded to the amide nitrogen througha C—N bond.

The term “metathesis catalyst” refers to any catalyst or catalyst systemconfigured to catalyze a metathesis reaction.

The terms “metathesize” and “metathesizing” refer to a chemical reactioninvolving a single type of olefin or a plurality of different types ofolefin, which is conducted in the presence of a metathesis catalyst, andwhich results in the formation of at least one new olefin product. Thephrase “metathesis reaction” encompasses cross-metathesis (a.k.a.co-metathesis), self-metathesis, ring-opening metathesis (ROM),ring-opening metathesis polymerizations (ROMP), ring-closing metathesis(RCM), and acyclic diene metathesis (ADMET), and the like, andcombinations thereof.

The terms “natural oils,” “natural feedstocks,” or “natural oilfeedstocks” mean oils derived from plants or animal sources. The term“natural oil” includes natural oil derivatives, unless otherwiseindicated. The terms also include modified plant or animal sources(e.g., genetically modified plant or animal sources), unless indicatedotherwise. Examples of natural oils include but are not limited tovegetable oils, algal oils, animal fats, tall oils, derivatives of theseoils, combinations of any of these oils, and the like. Examples ofvegetable oils include but are not limited to canola oil, rapeseed oil,coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil,safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palmkernel oil, tung oil, jatropha oil, mustard oil, camelina oil,pennycress oil, castor oil, and the like, and combinations thereof.Examples of animal fats include but are not limited to lard, tallow,poultry fat, yellow grease, fish oil, and the like, and combinationsthereof. Tall oils are by-products of wood pulp manufacture. A naturaloil may be refined, bleached, and/or deodorized.

The term “natural oil derivatives” refers to compounds or mixtures ofcompounds derived from one or more natural oils using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, transesterification, esterification,hydrogenation (partial or full), isomerization, oxidation, reduction,and the like, and combinations thereof. Examples of natural oilderivatives include but are not limited to gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl esters such as 2-ethylhexyl ester,hydroxy-substituted variations thereof of the natural oil, and the like,and combinations thereof. For example, the natural oil derivative may bea fatty acid methyl ester (FAME) derived from the glyceride of thenatural oil.

The term “metathesized natural oil” refers to the metathesis reactionproduct of a natural oil in the presence of a metathesis catalyst, wherethe metathesis product includes a new olefinic compound. A metathesizednatural oil may include a reaction product of two triglycerides in anatural feedstock (self-metathesis) in the presence of a metathesiscatalyst, where each triglyceride has an unsaturated carbon-carbondouble bond, and where the reaction product includes a “natural oiloligomer” having a new mixture of olefins and esters that may includeone or more of metathesis monomers, metathesis dimers, metathesistrimers, metathesis tetramers, metathesis pentamers, and higher ordermetathesis oligomers (e.g., metathesis hexamers). A metathesized naturaloil may include a reaction product of a natural oil that includes morethan one source of natural oil (e.g., a mixture of soybean oil and palmoil). A metathesized natural oil may include a reaction product of anatural oil that includes a mixture of natural oils and natural oilderivatives. A metathesized natural oil may include a cross-metathesisreaction product of a natural oil with another substance having acarbon-carbon double bond, such as an olefin or ethylene.

The term “polymeric” refers to a substance that includes a polymer.

The term “polymer” refers to a substance having a chemical structurethat includes the multiple repetition of constitutional units formedfrom substances of comparatively low relative molecular mass relative tothe molecular mass of the polymer. The term “polymer” includes solubleand/or fusible molecules having chains of repeat units, and alsoincludes insoluble and infusible networks.

The term “monomer” refers to a substance that can undergo apolymerization reaction to contribute constitutional units to thechemical structure of a polymer.

The term “prepolymer” refers to a polymer that can undergo furtherreaction to contribute constitutional units to the chemical structure ofa different polymer. The definitions for “polymer”, “monomer” and“prepolymer” are derived from IUPAC, Pure Appl. Chem., Vol. 68, No. 8,pp. 1591-1595, 1996.

Compounds having a plurality of (meth)acrylate functional groups may beformed from a renewable feedstock, such as a renewable feedstock formedthrough metathesis reactions of natural oils and/or their fatty acid orfatty ester derivatives. When compounds containing a carbon-carbondouble bond undergo metathesis reactions in the presence of a metathesiscatalyst, some or all of the original carbon-carbon double bonds arebroken, and new carbon-carbon double bonds are formed. The products ofsuch metathesis reactions include carbon-carbon double bonds indifferent locations, which can provide unsaturated organic compoundshaving useful chemical structures. Renewable feedstocks for compoundshaving a plurality of (meth)acrylate functional groups may includeunsaturated compounds having an internal carbon-carbon double bond.

Compounds having a plurality of (meth)acrylate functional groups may beused as monomers in polymerization reactions. The use of a monomercontaining a metathesized natural oil derivative can provide additionaloptions for providing polymeric materials having useful combinations ofproperties, including but not limited to mechanical properties,crosslink density, and post-polymerization reactivity. The compoundshaving a plurality of (meth)acrylate functional groups also may be usedas intermediates for preparing larger compounds through the reaction ofone or more of the plurality of (meth)acrylate functional groups withanother substance. The use of a monomer and/or an intermediatecontaining a metathesized natural oil derivative may provide certainadvantages over commercial monomers and intermediates, including but notlimited to simpler and/or more cost-effective production, reducedvariability, improved sourcing, and increased biorenewability.

A compound having a plurality of (meth)acrylate functional groups may bea ((meth)acryloylalkyl)amide represented by Structure I:

where R₁ and R₂ independently are C₂-C₁₂ alkyl groups, R₃ and R₃′independently are either H or CH₃, X₁ is a C₄-C₂₈ alkyl or alkenylgroup, and R₄ is selected from the group consisting of H and aN,N-bis((meth)acryloylalkyl)amide group represented by Structure II:

where R₅ and R₆ independently are C₂-C₁₂ alkyl groups, and R₃″ and R₃′″independently are either H or CH₃.

Preferably R₁, R₂, R₅ and R₆ independently are C₂-C₁₀ alkyl groups,C₂-C₈ alkyl groups, C₂-C₆ alkyl groups or C₂-C₄ alkyl groups. In oneexample, R₁, R₂, R₅ and R₆ are the same, and are a C₂-C₁₀ alkyl group, aC₂-C₈ alkyl group, a C₂-C₆ alkyl group, or a C₂-C₄ alkyl group.

Preferably X₁ is a C₈-C₂₂ alkyl or alkenyl group, or a C₁₀-C₁₆ alkyl oralkenyl group. X₁ may be derived from a natural oil, and preferably isderived from a metathesized natural oil.

In one example, R₁ and R₂ are C₂ alkyl groups, R₃ and R₃′ are CH₃, andR₄ is H. A compound having a plurality of (meth)acrylate functionalgroups according to this example may be a bis(methacryloylethyl)amiderepresented by Structure III:

where X₂ is a C₄-C₂₈ alkyl or alkenyl group. Preferably X₂ is a C₈-C₂₂alkyl or alkenyl group, or a C₁₀-C₁₆ alkyl or alkenyl group. X₂ may bederived from a natural oil, and preferably is derived from ametathesized natural oil.

In another example, R₁ and R₂ are C₂ alkyl groups, R₄ is abis((meth)acryloylalkyl)amide group represented by Structure (II), R₅and R₆ are C₂ alkyl groups, and R₃, R₃′, R₃″ and R₃′″ are CH₃. Acompound having a plurality of (meth)acrylate functional groupsaccording to this example may be a tetra(methacryloylethyl)diamiderepresented by Structure IV:

where X₃ is a C₄-C₂₈ alkyl or alkenyl group. Preferably X₃ is a C₈-C₂₂alkyl or alkenyl group, or a C₁₀-C₁₆ alkyl or alkenyl group. X₃ may bederived from a natural oil, and preferably is derived from ametathesized natural oil.

Preferably the compound having a plurality of (meth)acrylate functionalgroups is derived from a natural oil. More preferably the compoundhaving a plurality of (meth)acrylate functional groups is derived from ametathesized natural oil. Preferably the compound having a plurality of(meth)acrylate functional groups is the reaction product of a(hydroxyalkyl)amide and a (meth)acryloyl halide, where the(hydroxyalkyl)amide is a reaction product of a metathesized natural oiland a bis(hydroxyalkyl)amine. In one example, a metathesized natural oilderivative having a plurality of (meth)acrylate functional groups may berepresented by Structure I, III or IV, above.

The metathesized natural oil used to form the compound having aplurality of (meth)acrylate functional groups may be the product of ametathesis reaction of a natural oil in the presence of a metathesiscatalyst. The metathesis catalyst in this reaction may include anycatalyst or catalyst system that catalyzes a metathesis reaction. Anyknown metathesis catalyst may be used, alone or in combination with oneor more additional catalysts. Examples of metathesis catalysts andprocess conditions are described in paragraphs [0069]-[0155] of US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a transitionmetal. In some embodiments, the metathesis catalyst includes ruthenium.In some embodiments, the metathesis catalyst includes rhenium. In someembodiments, the metathesis catalyst includes tantalum. In someembodiments, the metathesis catalyst includes nickel. In someembodiments, the metathesis catalyst includes tungsten. In someembodiments, the metathesis catalyst includes molybdenum.

In some embodiments, the metathesis catalyst includes a rutheniumcarbene complex and/or an entity derived from such a complex. In someembodiments, the metathesis catalyst includes a material selected fromthe group consisting of a ruthenium vinylidene complex, a rutheniumalkylidene complex, a ruthenium methylidene complex, a rutheniumbenzylidene complex, and combinations thereof, and/or an entity derivedfrom any such complex or combination of such complexes. In someembodiments, the metathesis catalyst includes a ruthenium carbenecomplex including at least one phosphine ligand and/or an entity derivedfrom such a complex. In some embodiments, the metathesis catalystincludes a ruthenium carbene complex including at least onetricyclohexylphosphine ligand and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aruthenium carbene complex including at least two tricyclohexylphosphineligands [e.g., (PCy₃)₂Cl₂Ru═CH—CH═C(CH₃)₂, etc.] and/or an entityderived from such a complex. In some embodiments, the metathesiscatalyst includes a ruthenium carbene complex including at least oneimidazolidine ligand and/or an entity derived from such a complex. Insome embodiments, the metathesis catalyst includes a ruthenium carbenecomplex including an isopropyloxy group attached to a benzene ringand/or an entity derived from such a complex.

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

Metathesis is a catalytic reaction that involves the interchange ofalkylidene units among compounds containing one or more double bonds(i.e., olefinic compounds) via the formation and cleavage of thecarbon-carbon double bonds. The metathesis reaction of a natural oilcontaining unsaturated polyol esters can produce oligomers of theunsaturated polyol esters. The resulting oligomers typically contain amixture of olefins and esters that may include one or more of metathesismonomers, metathesis dimers, metathesis trimers, metathesis tetramers,metathesis pentamers, and higher order metathesis oligomers (e.g.,metathesis hexamers, etc.). FIG. 1 depicts chemical structures andreaction schemes related to a metathesis reaction 100 of a natural oil110, producing metathesis dimer 120, metathesis trimer 130 and higherorder metathesis oligomers (not pictured). A metathesis dimer refers toa compound formed when two unsaturated polyol ester molecules arecovalently bonded to one another by a metathesis reaction. The molecularweight of the metathesis dimer typically is greater than the molecularweight of the individual unsaturated polyol ester molecules from whichthe dimer is formed. A metathesis trimer refers to a compound formedwhen three unsaturated polyol ester molecules are covalently bondedtogether by metathesis reactions. A metathesis trimer may be formed bythe cross-metathesis of a metathesis dimer with an unsaturated polyolester. A metathesis tetramer refers to a compound formed when fourunsaturated polyol ester molecules are covalently bonded together bymetathesis reactions. A metathesis tetramer may be formed by thecross-metathesis of a metathesis trimer with an unsaturated polyolester. Metathesis tetramers may also be formed, for example, by thecross-metathesis of two metathesis dimers. Higher order metathesisoligomers (such as metathesis pentamers, metathesis hexamers, and thelike) also may be formed.

The metathesized natural oil may be derived from natural oils such asvegetable oil, algal oil, animal fat, tall oil, derivatives of theseoils, or mixtures thereof. Examples of vegetable oils include but arenot limited to canola oil, rapeseed oil, coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard oil, camelina oil, pennycress oil, castor oil, andthe like, and combinations thereof. Examples of animal fats include butare not limited to lard, tallow, poultry fat, yellow grease, fish oil,and the like, and combinations thereof. Examples of natural oilderivatives include but are not limited to metathesis oligomers, gums,phospholipids, soapstock, acidulated soapstock, distillate or distillatesludge, fatty acids and fatty acid alkyl ester such as 2-ethylhexylester, hydroxyl-substituted variations of the natural oil, and the like,and combinations thereof. For example, the natural oil derivative may bea fatty acid methyl ester (FAME) derived from the glyceride of thenatural oil.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

The metathesized natural oil may be a metathesized vegetable oil, ametathesized algal oil, a metathesized animal fat, a metathesized talloil, a metathesized derivatives of these oils, or a mixture thereof. Forexample, a metathesized vegetable oil may include metathesized canolaoil, metathesized rapeseed oil, metathesized coconut oil, metathesizedcorn oil, metathesized cottonseed oil, metathesized olive oil,metathesized palm oil, metathesized peanut oil, metathesized saffloweroil, metathesized sesame oil, metathesized soybean oil, metathesizedsunflower oil, metathesized linseed oil, metathesized palm kernel oil,metathesized tung oil, metathesized jatropha oil, metathesized mustardoil, metathesized camelina oil, metathesized pennycress oil,metathesized castor oil, metathesized derivatives of these oils, ormixtures thereof. In another example, the metathesized natural oil mayinclude a metathesized animal fat, such as metathesized lard,metathesized tallow, metathesized poultry fat, metathesized fish oil,metathesized derivatives of these oils, or mixtures thereof.

FIG. 2 depicts a method 200 of making a ((meth)acryloylalkyl)amidecomposition. The method 200 includes forming 201 a first reactionmixture 210 containing a metathesized natural oil 212 and abis(hydroxyalkyl)amine 214; forming 202 a first product mixture 220containing a (hydroxyalkyl)amide 222 formed from the metathesizednatural oil 212 and the bis(hydroxyalkyl)amine 214; forming 203 a secondreaction mixture 230 containing the (hydroxyalkyl)amide 222 and a(meth)acryloyl halide 234; forming 204 a second product mixture 240containing a ((meth)acryloylalkyl)amide 242 formed from the(hydroxyalkyl)amide 222 and the (meth)acryloyl halide 234; andoptionally isolating 205 the ((meth)acryloylalkyl)amide 242 from thesecond product mixture 240.

The metathesized natural oil 212 in the first reaction mixture 210 maybe a metathesized vegetable oil, a metathesized algal oil, ametathesized animal fat, a metathesized tall oil, a metathesizedderivatives of these oils, or a mixture thereof, as described above.Preferably the metathesized natural oil 212 includes metathesizedsoybean oil (MSBO).

The bis(hydroxyalkyl)amine 214 may be a secondary amine that includestwo hydroxyalkyl groups bonded to the amine nitrogen through C—N bonds.The bis(hydroxyalkyl)amine 214 may be represented by Structure V:

where R₁ and R₂ are as described above regarding Structure I. The twohydroxyalkyl groups (—R₁—OH and —R₂—OH) may be the same, or they may bedifferent. The hydroxyl group may be at any of a number of positionswithin the hydroxyalkyl group. Preferably at least one of thehydroxyalkyl groups is a o-hydroxyalkyl group, in which the hydroxylgroup is at the end of the hydroxyalkyl group opposite that of the C—Nbond to the secondary amine nitrogen. Examples ofbis(hydroxyalkyl)amines include bis(2-hydroxypropyl)amine andN-2-hydroxypropyl-N-hydroxyethylamine. Examples ofbis(ω-hydroxyalkyl)amines include but are not limited to diethanolamine.Preferably the bis(hydroxyalkyl)amine 214 includes diethanolamine.

In some embodiments, the amount of bis(hydroxyalkyl)amine present in thefirst reaction mixture 210 may be between about 0.1 percent by weight(wt %) and about 30 wt % of the metathesized natural oil in the reactionmixture. The amount of bis(hydroxyalkyl)amine in the reaction mixturealso may be expressed in terms of the ratio of equivalents of amine inthe bis(hydroxyalkyl)amine to ester equivalents in the metathesizednatural oil (A:E ratio). For example, in some embodiments, the A:E ratiomay be between about 1:100 and about 10:1, or between about 1:10 andabout 5:1. In another example, the A:E ratio may be about 1:3, about2:3, about 1:2, or about 1:1.

The first reaction mixture 210 may include one or more other substances,such as a solvent, a base and/or a catalyst, in addition to themetathesized natural oil 212 and a bis(hydroxyalkyl)amine 214. Themetathesized natural oil 212, bis(hydroxyalkyl)amine 214 and optionalother substances may be combined simultaneously or in any order.

In one example, the first reaction mixture 210 includes a base toincrease the rate of reaction between the bis(hydroxyalkyl)amine and themetathesized natural oil. Examples of bases include but are not limitedto sodium carbonate, lithium carbonate, sodium methoxide, potassiumhydroxide, sodium hydride, potassium butoxide, potassium carbonate, ormixtures of these. The base may be added to the first reaction mixture210 neat or as a mixture with a solvent such as water, alcohol, oranother organic solvent. In some embodiments, the amount of base in thereaction mixture may be between about 0.1 wt % and about 10 wt % of themetathesized natural oil in the reaction mixture, or between about 1 wt% and about 15 wt % of the metathesized natural oil. In someembodiments, the amount of base in the reaction mixture may be betweenabout 1 wt % and about 10 wt % of the metathesized natural oil, betweenabout 0.1 wt % and about 1.0 wt % of the metathesized natural oil, orbetween about 0.01 wt % and about 0.1 wt % of the metathesized naturaloil.

The forming 202 a first product mixture 220 containing a(hydroxyalkyl)amide 222 may include heating the first reaction mixture210. In some embodiments, the rate of reaction between thebis(hydroxyalkyl)amine 214 and the metathesized natural oil 212 may beincreased by heating the reaction mixture, with or without a base, to atleast about 100° C., at least about 120° C., at least about 140° C., atleast about 160° C., or between about 100° C. and about 200° C. In someembodiments, the reaction may be carried out at an elevated temperatureof between about 30 and about 250° C., between about 80 and about 150°C., or between about 100 and about 125° C. In some embodiments, thereaction mixture may be maintained at the elevated temperature for atime sufficient to form a (hydroxyalkyl)amide 222, such as between about1 and about 24 hours, or between about 4 and about 24 hours. Forexample, the reaction mixture may be maintained at the elevatedtemperature for about 1 hour, about 2 hours, about 4 hours, or about 6hours. In some embodiments, the reaction may be carried out in an inertatmosphere, such as a nitrogen atmosphere or a noble gas atmosphere. Insome embodiments, the reaction may be carried out in an ambientatmosphere.

In some embodiments, heating the first reaction mixture may includemaintaining the reaction mixture at a temperature of from about 30° C.to about 150° C. In some embodiments, the reaction mixture temperaturemay be from about 30° C. to about 100° C., or from about 50° C. to about85° C. In some embodiments, the reaction mixture may be maintained at atemperature within these ranges for a period of from about 1 hour toabout 48 hours, including but not limited to from about 1 hour to about24 hours, and from about 2 hours to about 8 hours. A (hydroxyalkyl)amide222 may be formed at a lower temperature and/or within a shorter periodof time if the reaction mixture 210 includes a catalyst.

The (hydroxyalkyl)amide 222 may be represented by Structure VI:

where R₁, R₂, R₅, R₆ and X₁ are as described above regarding StructureI. The (hydroxyalkyl)amide 222 reaction product may have one chemicalstructure, or the reaction product may be a mixture of compounds havingdifferent chemical structures.

The (hydroxyalkyl)amide 222 reaction product optionally may be isolatedfrom the first product mixture 220, such as by removing volatilesubstances under vacuum. For example, the reaction mixture may be placedunder a vacuum for between about 30 minutes and about 1 hour. Volatilesubstances may include but are not limited to water, solvent, unreactedbis(hydroxyalkyl)amine, and/or glycerol. For a reaction product thatincludes a mixture of compounds having different chemical structures,individual compounds may be isolated from the reaction product, or thereaction product may be used as a mixture.

The forming 203 a second reaction mixture 230 includes combining the(hydroxyalkyl)amide 222 and a (meth)acryloyl halide 234. The(meth)acryloyl halide 234 may be methacryloyl chloride, methacryloylbromide, methacryloyl iodide, acryloyl chloride, acryloyl bromide oracryloyl iodide. The second reaction mixture 230 also may include one ormore other substances, such as a solvent and/or a tertiary amine. The(hydroxyalkyl)amide 222, (meth)acryloyl halide 234 and optional tertiaryamine and/or solvent may be combined simultaneously or in any order.

In some embodiments, a tertiary amine may be present in the secondreaction mixture 230 to remove halide salt reaction products from thereaction mixture, facilitating the progress of the reaction to yield the((meth)acryloylalkyl)amide product 242. Examples of tertiary aminesinclude but are not limited to trimethylamine, triethylamine,tripropylamine, tributylamine, or mixtures of these. Preferably themolar amount of the tertiary amine is greater than or approximatelyequal to the molar amount of the (meth)acryloyl halide 234. The tertiaryamine may be added to the reaction mixture neat or as a mixture with asolvent such as water, alcohol, or another organic solvent.

In some embodiments, the amount of (meth)acryloyl halide 234 present inthe reaction mixture may be between about 50 percent by weight (wt %)and about 100 wt % of the (hydroxyalkyl)amide 222 in the reactionmixture. The amount of (meth)acryloyl halide in the reaction mixturealso may be expressed in terms of the ratio of equivalents of halide tohydroxyl equivalents in the (hydroxyalkyl)amide. For example, in someembodiments, the halide:hydroxyl ratio may be between about 1:10 andabout 10:1, or between about 1:1 and about 2:1. In another example, theA:E ratio may be about 1:1, about 1.5:1, about 1.75:1, or about 2:1.

The forming 204 a second product mixture 240 containing a((meth)acryloylalkyl)amide product 242 may include heating the secondreaction mixture 230. In some embodiments, the rate of reaction betweenthe (hydroxyalkyl)amide 222 and the (meth)acryloyl halide 234 may beincreased by heating the reaction mixture, with or without a tertiaryamine to at least about 30° C., at least about 40° C., at least about50° C., at least about 75° C., or between about 30° C. and about 100° C.In some embodiments, the reaction between the (meth)acryloyl halide 234and the (hydroxyalkyl)amide 222 may be carried out at an elevatedtemperature of between about 30 and about 70° C., or between about 30and about 60° C.

In some embodiments, the second reaction mixture 240 may be maintained,either at room temperature (˜25° C.) or at an elevated temperature, fora time sufficient to form a ((meth)acryloylalkyl)amide 222, such asbetween about 1 and about 24 hours, between about 1 and about 12 hours,or between about 2 hours to about 8 hours. For example, the secondreaction mixture may be maintained at the elevated temperature for about1 hour, about 2 hours, about 4 hours, about 6 hours or about 8 hours. Insome embodiments, the reaction between the (meth)acryloyl halide 234 andthe (hydroxyalkyl)amide 222 may be carried out in an inert atmosphere,such as a nitrogen atmosphere or a noble gas atmosphere. In someembodiments, the reaction may be carried out in an ambient atmosphere. A((meth)acryloylalkyl)amide 242 may be formed at a lower temperatureand/or within a shorter period of time if the second reaction mixture230 includes a tertiary amine and/or a catalyst.

The optionally isolating 205 the ((meth)acryloylalkyl)amide 222 from thesecond product mixture 240 may include removing volatile substancesunder vacuum. For example, the product mixture may be placed under avacuum for between about 30 minutes and about 1 hour.

The ((meth)acryloylalkyl)amide 242 reaction product may have onechemical structure, or the reaction product may be a mixture ofcompounds having different chemical structures. For example, for the((meth)acryloylalkyl)amide 242 reaction product may include a mixture ofcompounds represented by Structure I. For a reaction product thatincludes a mixture of compounds having different chemical structures,individual compounds may be isolated from the reaction product, or thereaction product may be used as a mixture.

FIG. 3 depicts chemical structures and a reaction scheme for an exampleof a method 300 of making a ((meth)acryloylalkyl)amide composition. Themethod 300 includes forming a reaction mixture 310 containingmetathesized soybean oil (MSBO) 312 as the metathesized natural oil anddiethanolamine 314 as the bis(hydroxyalkyl)-amine. The reaction mixture310 also may include one or more other substances, such as a solvent, abase and/or a catalyst.

Method 300 further includes forming 302 a product mixture 320 containing(hydroxyethyl)amide species, such as 322 and/or 324. In species 322 and324, w, x, y and z independently are integers from 0 to 18, such thatthe total number of carbon atoms between the amido groups is from 6 to28, and the partially dashed double line indicates that species may ormay not include one or more carbon-carbon double bonds. The forming 302may include heating the reaction mixture as described above, includingmaintaining the reaction mixture at a temperature of from about 30° C.to about 150° C. for a time sufficient to form (hydroxyalkyl)amidespecies. The tetra(hydroxyethyl)diamide species 322 andbis(hydroxyethyl)amide species 324 are exemplary, as the product mixture320 may include a number of different species of (hydroxyethyl)amidesconsistent with Structure VI. Structural variables between the speciesinclude but are not limited to the presence and number of carbon-carbondouble bonds, the number of carbon atoms in the organic group bonded tothe (hydroxyethyl)amide group(s), and branching.

Method 300 further may include isolating a (hydroxyethyl)amide species.As noted above, isolating one or both of the (hydroxyethyl)amide speciesmay include removing volatile substances under vacuum where the volatilesubstances may include but are not limited to water, solvent, unreacteddiethanolamine 314, and/or glycerol. The optional isolating may providea mixture of (hydroxyethyl)amide species, or it may provide a single(hydroxyethyl)amide species.

Method 300 further includes forming 304 a product mixture 340 containing((meth)acryloylethyl)amide species, such as 342 and/or 344, where w, x,y and z are as described above with regard to species 322 and 324. Theforming 304 may include reacting the (hydroxyethyl)amide species 322and/or 324 with a (meth)acryloyl halide, such as methacryloyl chloride334. The forming 304 may include forming a reaction mixture containingthe (hydroxyethyl)amide species 322 and/or 324, a methacryloyl halideand optionally a tertiary amine, such as triethylamine 336. The forming304 occur at room temperature (˜25° C.), or it may include heating thereaction mixture as described above, including maintaining the reactionmixture at a temperature of from about 30° C. to about 150° C. for atime sufficient to form (methacryloylethyl)amide species. Thetetra(methacryloylethyl)diamide species 342 andbis(methacryloylethyl)amide species 344 are exemplary, as the productmixture 340 may include a number of different species of(methacryloylethyl)amides consistent with Structure I. Structuralvariables between the species include but are not limited to thepresence and number of carbon-carbon double bonds, the number of carbonatoms in the organic group bonded to the (methacryloylethyl)amidegroup(s), and branching.

Method 300 further may include isolating a ((meth)acryloylethyl)amidespecies. As noted above, isolating one or both of the((meth)acryloylethyl)amide species may include removing volatilesubstances under vacuum. The optional isolating may provide a mixture of((meth)acryloylethyl)amide species, or it may provide a single((meth)acryloylethyl)amide species.

A compound having a plurality of (meth)acrylate functional groups may beused in a polymerization reaction. Compounds having an acrylate or amethacrylate functional group may undergo addition polymerizationreactions. Compounds having an acrylate or a methacrylate functionalgroup also may undergo addition copolymerization reactions with othercompounds having terminal alkenyl groups. Monomers having a plurality of(meth)acrylate functional groups may be used as chain extenders, ascrosslinkers, or as branching points in a polymer.

FIG. 4 represents a method 400 of forming a polymer. The method 400includes forming 401 a polymerization mixture 410 containing a firstmonomer 412 having at least two (meth)acrylate functional groups, anoptional second monomer 414 having at least one alkenyl functionalgroup, and an optional polymerization initiator 416. The method furtherincludes forming 402 a product mixture 420 containing a polymer 422having constitutional units formed from the first monomer 412 andoptionally the second monomer 414.

The first monomer 412 having at least two (meth)acrylate functionalgroups may be a compound having a plurality of (meth)acrylate functionalgroups as described above. The first monomer may be represented by oneor more of Structures I, III and IV. The first monomer may be a reactionproduct of a (hydroxyalkyl)amide and a (meth)acryloyl halide, where the(hydroxyalkyl)amide is a reaction product of a metathesized natural oiland a bis(hydroxyalkyl)amine.

The optional second monomer 414 may include any polymerizable substancethat contains an alkenyl group. Examples of such unsaturatedpolymerizable substances include ethylene; styrenes such as styrene andmethyl styrene; halogenated vinyl compounds such as vinyl chloride,vinylidene chloride and tetrafluoroethylene; acrylates; acrylamide;acrylonitrile; N-vinyl pyrrolidone; and substituted derivatives thereof.Examples of acrylate monomers include butyl acrylate, 2-ethylhexylacrylate, ethyl acrylate, lauryl acrylate, hexadecyl acrylate, andmethacrylate derivatives of these monomers. Examples of acrylamidemonomers include acrylamide, N,N-dimethyl acrylamide, N-ethylacrylamide, N-isopropyl acrylamide and hydroxymethyl acrylamide, andmethacrylamide derivatives of these monomers.

The optional polymerization initiator 416 may include a free radicalpolymerization initiator, a cationic polymerization initiator, or ananionic polymerization initiator. A polymerization initiator is notrequired in the reaction mixture 410, however, as additionpolymerization may be initiated by heat or by electromagnetic radiationsuch as visible or ultraviolet light.

The polymerization mixture 410 may include only the monomer(s) andoptionally an initiator, or it may include one or more other substances,such as a solvent, a buffer or a salt. Examples of solvents include butare not limited to protic solvents such as water, methanol, ethanol,isopropyl alcohol (IPA) and butanol; and aprotic solvents such astetrahydrofuran (THF), dioxane, dimethyl formamide (DMF), toluene andxylene.

Preferably forming 401 the polymerization mixture 410 includes combiningthe monomers with a free radical addition polymerization initiator.Selection of a particular free radical polymerization initiator maydepend on a number of factors including but not limited to thepolymerization temperature, the type of comonomers, and whether asolvent is present in the reaction mixture. Examples of free radicalpolymerization initiators include but are not limited to peroxides suchas hydrogen peroxide; alkyl peroxides such as di-t-butyl peroxide,di-t-amyl peroxide, dilauroyl peroxide and2,5-bis(t-butylperoxy)-2,5-dimethylhexane; acyl peroxides; arylperoxides such as benzoyl peroxide, dicumyl peroxide and t-butylperoxybenzoate; and hydroperoxides such as t-butyl hydroperoxide.Examples of free radical polymerization initiators include but are notlimited to azo compounds such as 2,2′-azobisisobutyro-nitrile (AIBN),2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(2-amidino-propane)-dihydrochloride, and2,2′-azobis(N,N′-dimethylene-isobutylamidine). Examples of free radicalpolymerization initiators include but are not limited to persulfatessuch as potassium persulfate and ammonium persulfate. The amount ofpolymerization initiator may range, for example, from about 0.01 to 5mol % based on the total moles of comonomers present.

Forming 402 a product mixture 420 containing a polymer 422 havingconstitutional units formed from the first monomer 412 and optionallythe second monomer 414 may include heating the polymerization mixture.The polymerization mixture may be heated to a temperature of at leastabout 30° C., including but not limited to a temperature from about 30°C. to about 250° C., from about 40° C. to about 200° C., from about 50°C. to about 175° C., or from about 60° C. to about 160° C. Thepolymerization mixture may be heated for at least about 1 hour,including but not limited to from about 1 hour to about 100 hours, fromabout 5 hours to about 50 hours, from about 10 hours to about 30 hours,or from about 15 hours to about 25 hours.

Forming 402 a product mixture 420 may include isolating the polymer 422.Isolating the polymer 422 may include removing volatile startingmaterial and/or byproducts under reduced pressure and/or heat. Isolatingthe polymer 422 may include dissolving the polymer in a solvent to forma solution, and precipitating the polymer by contacting the solutionwith a non-solvent for the polymer. Isolating the polymer 422 mayinclude dissolving the polymer in a solvent to form a solution, andremoving low molecular weight species from the solution by dialysisagainst the solvent.

FIG. 5 depicts chemical structures and a reaction scheme for an exampleof a method 500 of forming a copolymer. Method 500 includes forming areaction mixture 510 containing first monomers 512 having at least twomethacrylate functional groups and a second monomer 514 having at leastone alkenyl functional group, and forming 502 a product mixture 520containing a copolymer 522 having constitutional units formed from thefirst monomers 512 and the second monomer 514.

In the first monomers 512 and in the copolymer 522, X₂ and X₃ are asdescribed above for Structures III and IV. The second monomer 514depicted in FIG. 5 is methyl methacrylate. In the copolymer 522,x+y+z=1, and n may be from 2 to 100, from 3 to 50, or from 4 to 25. The“

” symbol represents a potential linkage to another polymer chain.

A compound having a plurality of (meth)acrylate functional groups, suchas the reaction product of a metathesized natural oil and abis(aminoalkyl) amine and/or a compound represented by Structure Iabove, may be used to form a dendritic molecule. In one example, thecompound having a plurality of (meth)acrylate functional groups may beused as a substitute for some or all of the methyl acrylate typicallyused in the synthesis of PAMAM dendrimers. In another example, thecompound having a plurality of (meth)acrylate functional groups may beused as the core in the divergent synthesis of a dendrimer. Reaction ofthe compound with ethylenediamine, followed by reaction with methylacrylate, may provide a dendrimer analogous to the PAMAM system, butwith a core that is more flexible and less sterically hindered.

The following examples and representative procedures illustrate featuresin accordance with the present teachings, and are provided solely by wayof illustration. They are not intended to limit the scope of theappended claims or their equivalents, and numerous variations can bemade to the following examples that lie within the scope of theseclaims.

EXAMPLES Example 1: Formation of (Hydroxyalkyl)Amide Compounds

Compounds having at least two hydroxyl functional groups were formed byreacting a metathesized natural oil and a bis(hydroxyalkyl)amine.Diethanolamine (150 grams (g)) and potassium t-butoxide (3.5 g) werecombined in a flask equipped with a condenser, and the mixture washeated to 115° C. and stirred. To this mixture, metathesized soybean oil(MSBO; 400 g) was added dropwise. Table 1 lists the reactants present inthe reaction mixture.

TABLE 1 Reactants used to form compound having at least two hydroxylgroups Diethanol- potassium MSBO amine t-butoxide molecular weight 200* 105.14 g/mol 112.21 g/mol mass 400 g 150 g 3.5 g moles    1.426 1.4270.312 equivalents 1 1 0.022 *saponification value

The mixture was maintained at 115° C. for 1.5 hours after the MSBOaddition was complete. The mixture was allowed to cool, and was thendissolved in diethyl ether, washed with a saturated sodium chloridesolution, and dried. The ether was removed from the product by rotaryevaporation to provide a mixture of monomers having at least twohydroxyl functional groups and containing a group derived from the MSBO.

Characterization of the product by Fourier Transform InfraredSpectroscopy (FTIR) was consistent with full conversion of the estergroups in the MSBO to N,N-diethanolamide groups. The hydroxyl value(OHV) was determined to be 285, which corresponds to 5.079 millimoles ofhydroxyl groups per gram. While neither desiring to be bound by anyparticular theory nor intending to limit in any measure the scope of theappended claims or their equivalents, it is presently believed that theproduct may be represented by Structure VII:

where X₂ and X₃ are as described above with regard to Structures III andIV.

Example 2: Formation of ((Meth)Acryloylalkyl)Amide Compounds

Compounds having at least two (meth)acrylate functional groups wereformed by reacting the (hydroxyalkyl)amide compounds of Example 1 and a(meth)acryloyl halide. In a flask containing dichloromethane, 30 g ofthe product of Example 1 was dissolved. Methacryloyl chloride (19.87 g)and triethylamine (19.24 g) were added to this solution, and the mixturewas stirred for approximately 12 hours at room temperature (˜25° C.).Table 2 lists the reactants present in the reaction mixture.

TABLE 2 Reactants used to form compound having at least two methacrylategroups (Hydroxy- Methacryloyl alkyl)amides chloride Triethylaminemolecular weight 285*  104.54 g/mol 101.10 g/mol mass 30 g 19.87 g 19.24g moles    0.1524 0.1905 0.1905 equivalents 1 1.25 1.25 *hydroxyl value(OHV)

The mixture was washed with a saturated sodium chloride solution, andthe organic layer was dried over sodium sulfate. The dichloromethanesolvent was removed from the product by rotary evaporation, and theproduct was washed in methanol. The resulting product (33.8 g) was anamber liquid.

Characterization of the product by Fourier Transform InfraredSpectroscopy (FTIR) was consistent with full conversion of the hydroxylgroups in the (hydroxyalkyl)amide compounds to methacryloyl groups.While neither desiring to be bound by any particular theory norintending to limit in any measure the scope of the appended claims ortheir equivalents, it is presently believed that the product may berepresented by Structures III and IV, where the X₂ and X₃ groups arealkyl groups or alkenyl groups from the MSBO.

The ability of the methacrylate functional groups in the reactionproduct to polymerize was confirmed by storing the product in a clearglass jar at room temperature, without protecting the product fromambient light sources. After 60 hours, the product had transformed froma liquid to a solid, which was insoluble.

Example 3: Formation of Poly(Methyl Methacrylate) and of CopolymersContaining Methyl Methacrylate Units and ((Meth)Acryloylalkyl)AmideUnits

A polymer was formed by polymerizing a first monomer having at least one(meth)acrylate group, and copolymers were formed by copolymerizing thefirst monomer and a second monomer having at least two (meth)acrylategroups, where the second monomer is a derivative of a metathesizednatural oil. Methyl methacrylate was polymerized by free radicalpolymerization to form poly(methyl methacrylate), and was copolymerizedwith the ((meth)acryloylalkyl)amide compounds of Example 2. Thepolymerization/copolymerization reactions were carried out by formingpolymerization mixtures containing tetrahydrofuran solvent (THF), methylmethacrylate (MMA), azoisobutyronitrile initiator (AIBN) and optionallya portion of the reaction product of Example 2. Table 3 lists theamounts of methacrylate and (methacryloylalkyl)amide present in thepolymerization mixtures. Each polymerization mixture also included 4.446g THF solvent and 0.14 g AIBN initiator (0.3 wt % of MMA). The percentof (methacryloylalkyl)amide listed is the weight percent with regard tothe total mass of methacrylate-functionalized monomers.

TABLE 3 Methacrylate-functionalized monomers used to form polymers andcopolymers Methyl methacrylate (Methacryloylalkyl)amide (g) (g)(percent*) A 4.7 g — 0 wt % B 4.7 g 11.7 mg 0.25 wt % C 4.7 g 23.5 mg0.50 wt % D 4.7 g 47 mg 1.0 wt %

The polymerization mixtures were placed in vials, sparged with nitrogenand/or argon gas for 15 seconds, and then sealed and heated at 60° C.for 8 hours. The resulting product was dissolved in dichloromethane, andthe polymer was precipitated by pouring the liquid into methanol.

The foregoing detailed description and accompanying drawings have beenprovided by way of explanation and illustration, and are not intended tolimit the scope of the appended claims. Many variations in the presentlypreferred embodiments illustrated herein will be apparent to one ofordinary skill in the art, and remain within the scope of the appendedclaims and their equivalents.

It is to be understood that the elements and features recited in theappended claims may be combined in different ways to produce new claimsthat likewise fall within the scope of the present invention. Thus,whereas the dependent claims appended below depend from only a singleindependent or dependent claim, it is to be understood that thesedependent claims can, alternatively, be made to depend in thealternative from any preceding claim—whether independent or dependentand that such new combinations are to be understood as forming a part ofthe present specification.

1-31. (canceled)
 32. A method of forming a (meth)acrylate natural oilderivative, comprising: providing a natural oil composition comprisingunsaturated glycerides; reacting the unsaturated glycerides of thenatural oil composition in the presence of a metathesis catalyst to formglyceride oligomers; reacting the glyceride oligomers of with abis(hydroxyalkyl) amine to form bis(hydroxyalkyl) amidated glycerideoligomers; and reacting the bis(hydroxyalkyl) amidated glycerideoligomers with an acryloyl halide, a methacryloyl halide, or acombinations thereof, to form the (meth)acrylate natural oil derivative.33. The method of claim 32, wherein the natural oil compositioncomprises vegetable oil, algal oil, animal fat, tall oil, or anymixtures thereof.
 34. The method of claim 33, wherein the natural oilcomposition comprises vegetable oil.
 35. The method of claim 34, whereinthe vegetable oil is canola oil, rapeseed oil, coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard oil, camelina oil, pennycress oil, castor oil, andany combinations thereof.
 36. The method of claim 35, wherein thevegetable oil is soybean oil.
 37. The method of claim 32, wherein theglyceride oligomers comprise metathesis dimers of unsaturatedglycerides, metathesis trimers of unsaturated glycerides, metathesistetramers of unsaturated glycerides, metathesis pentamers of unsaturatedglycerides, metathesis hexamers of unsaturated glycerides, or anycombinations thereof.
 38. The method of claim 32, wherein thebis(hydroxyalkyl) amine is diethanolamine.
 39. The method of claim 32,wherein the metathesized natural oil derivative is formed by reactingthe bis(hydroxyalkyl) amidated glyceride oligomers with an acryloylhalide.
 40. The method of claim 39, wherein the acryloyl halide isacryloyl chloride, acryloyl bromide, acryloyl iodide, or anycombinations thereof.
 41. The method of claim 32, wherein themetathesized natural oil derivative is formed by reacting thebis(hydroxyalkyl) amidated glyceride oligomers with an methacryloylhalide.
 42. The method of claim 41, wherein the methacryloyl halide ismethacryloyl chloride, methacryloyl bromide, methacryloyl iodide, or anycombinations thereof.
 43. A method of forming a (meth)acrylate polymer,comprising: providing a reactant composition comprising a first monomer,which is a (meth)acrylate natural oil derivative formed by the method ofclaim 32, and a polymerization initiator; and forming a (meth)acrylatepolymer comprising one or more constitutional units formed from thefirst monomer.
 44. The method of claim 43, wherein the reactantcomposition further comprises a second monomer, and wherein the(meth)acrylate polymer further comprises one or more constitutionalunits formed from the second monomer.
 45. The method of claim 44,wherein the second monomer is selected from the group consisting of:ethylene, styrenes, halogenated vinyl compounds, acrylates, acrylamide,acrylonitrile, N-vinyl pyrrolidone, and combinations thereof.
 46. Themethod of claim 43, wherein the polymerization initiator is free-radicalpolymerization initiator, a cationic polymerization initiator, ananionic polymerization initiator, or any combinations thereof.